Parametrization of atomic energies to improve small basis set density functional thermochemistry

Edward Brothers, Gustavo E. Scuseria

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Enthalpies of formation predicted with density functional theory and small basis sets can be greatly improved by treating the atomic energies as empirical parameters. When a variety of functionals and small basis sets are used, the root-mean-square error in enthalpies of formation is reduced by a factor of approximately two for the least improved functional/basis set pair, with significantly larger reductions for other functionals, especially LSDA. When the 3-21G* and 3-21+G* basis sets are used with nonempirical functionals, it is possible to achieve accuracy greater than that of PM3, which was primarily designed to reproduce enthalpies of formation. In addition to decreasing statistical errors, our procedure can also remove qualitative errors in density functional/basis set pairs that fail for the prediction of enthalpies of formation.

Original languageEnglish
Pages (from-to)1045-1049
Number of pages5
JournalJournal of Chemical Theory and Computation
Volume2
Issue number4
DOIs
Publication statusPublished - 2006
Externally publishedYes

Fingerprint

Thermochemistry
thermochemistry
nuclear energy
Nuclear energy
Enthalpy
enthalpy
functionals
root-mean-square errors
Mean square error
Density functional theory
density functional theory
predictions

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Parametrization of atomic energies to improve small basis set density functional thermochemistry. / Brothers, Edward; Scuseria, Gustavo E.

In: Journal of Chemical Theory and Computation, Vol. 2, No. 4, 2006, p. 1045-1049.

Research output: Contribution to journalArticle

@article{f1b55835d2144adb86347774f78e7ce4,
title = "Parametrization of atomic energies to improve small basis set density functional thermochemistry",
abstract = "Enthalpies of formation predicted with density functional theory and small basis sets can be greatly improved by treating the atomic energies as empirical parameters. When a variety of functionals and small basis sets are used, the root-mean-square error in enthalpies of formation is reduced by a factor of approximately two for the least improved functional/basis set pair, with significantly larger reductions for other functionals, especially LSDA. When the 3-21G* and 3-21+G* basis sets are used with nonempirical functionals, it is possible to achieve accuracy greater than that of PM3, which was primarily designed to reproduce enthalpies of formation. In addition to decreasing statistical errors, our procedure can also remove qualitative errors in density functional/basis set pairs that fail for the prediction of enthalpies of formation.",
author = "Edward Brothers and Scuseria, {Gustavo E.}",
year = "2006",
doi = "10.1021/ct600109x",
language = "English",
volume = "2",
pages = "1045--1049",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Parametrization of atomic energies to improve small basis set density functional thermochemistry

AU - Brothers, Edward

AU - Scuseria, Gustavo E.

PY - 2006

Y1 - 2006

N2 - Enthalpies of formation predicted with density functional theory and small basis sets can be greatly improved by treating the atomic energies as empirical parameters. When a variety of functionals and small basis sets are used, the root-mean-square error in enthalpies of formation is reduced by a factor of approximately two for the least improved functional/basis set pair, with significantly larger reductions for other functionals, especially LSDA. When the 3-21G* and 3-21+G* basis sets are used with nonempirical functionals, it is possible to achieve accuracy greater than that of PM3, which was primarily designed to reproduce enthalpies of formation. In addition to decreasing statistical errors, our procedure can also remove qualitative errors in density functional/basis set pairs that fail for the prediction of enthalpies of formation.

AB - Enthalpies of formation predicted with density functional theory and small basis sets can be greatly improved by treating the atomic energies as empirical parameters. When a variety of functionals and small basis sets are used, the root-mean-square error in enthalpies of formation is reduced by a factor of approximately two for the least improved functional/basis set pair, with significantly larger reductions for other functionals, especially LSDA. When the 3-21G* and 3-21+G* basis sets are used with nonempirical functionals, it is possible to achieve accuracy greater than that of PM3, which was primarily designed to reproduce enthalpies of formation. In addition to decreasing statistical errors, our procedure can also remove qualitative errors in density functional/basis set pairs that fail for the prediction of enthalpies of formation.

UR - http://www.scopus.com/inward/record.url?scp=33846190142&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33846190142&partnerID=8YFLogxK

U2 - 10.1021/ct600109x

DO - 10.1021/ct600109x

M3 - Article

VL - 2

SP - 1045

EP - 1049

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 4

ER -